CN109678108A - Lithium-sulfur cell - Google Patents

Lithium-sulfur cell Download PDF

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Publication number
CN109678108A
CN109678108A CN201710973029.1A CN201710973029A CN109678108A CN 109678108 A CN109678108 A CN 109678108A CN 201710973029 A CN201710973029 A CN 201710973029A CN 109678108 A CN109678108 A CN 109678108A
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CN
China
Prior art keywords
lithium
sulfur cell
diaphragm
cathode
mop
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Granted
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CN201710973029.1A
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CN109678108B (en
Inventor
罗宇峰
王佳平
范守善
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Priority to CN201710973029.1A priority Critical patent/CN109678108B/en
Priority to TW106136805A priority patent/TWI667833B/en
Priority to US16/143,506 priority patent/US10714728B2/en
Publication of CN109678108A publication Critical patent/CN109678108A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of lithium-sulfur cells, it includes a cathode, one anode, a lithium-sulfur cell diaphragm and electrolyte, the electrolyte level is between cathode and anode, the lithium-sulfur cell diaphragm setting between a cathode and an anode, is located in electrolyte, wherein, the lithium-sulfur cell diaphragm includes a basic diaphragm and a functional layer, the functional layer include multiple MoP2Nano particle and multiple graphene films, the multiple MoP2Nano particle and multiple graphene films are mutually mixed and are uniformly distributed, and mutually overlap or are stacked between multiple graphene film, the integral graphene layer of shape, the multiple MoP2Nano particle is attached to the surface of multiple graphene films, when the lithium-sulfur cell diaphragm is applied to lithium-sulfur cell, the cathode setting of the functional layer face lithium-sulfur cell.

Description

Lithium-sulfur cell
Technical field
The present invention relates to a kind of lithium-sulfur cells.
Background technique
Lithium-sulfur cell is using sulphur simple substance as cathode, using lithium metal as anode.Anode reaction loses electronics for lithium and becomes when electric discharge Lithium ion, cathode reaction are that sulphur and lithium ion and electron reaction generate sulfide.Since multielectron transfer reaction occurs, It is up to 1672mAh/g (MAh/g) with very high theoretical specific capacity, specific capacity.In addition, since sulphur simple substance has environment The features such as small, nontoxic, at low cost and raw material sources are extensive is polluted, therefore, lithium-sulfur cell receives more and more attention.
Diaphragm is an important component in lithium-sulfur cell, for separating cathode and anode, to avoid internal short-circuit, Facilitate free lithium ion simultaneously to transport between the electrodes.Lithium-sulfur cell diaphragm is usually that polypropylene, polyethylene (PP/PE) etc. is non- Polarity film the, however, polysulfide (Li that lithium-sulfur cell generates during discharge2Sx, wherein 4≤x≤8) with highly polar Feature, and it is highly soluble in electrolyte.Parasitic reaction caused by polysulfide dissolves has seriously affected the cyclicity of Li-S battery Energy and coulombic efficiency.However, lithium-sulfur cell diaphragm in the prior art is difficult to inhibit polysulfide diffusion, and then make polysulfide It shuttles between a cathode and an anode, leads to the irreversible breaking of cathode sulfur-bearing structure.The shortcomings that above-mentioned diaphragm, leads to lithium-sulfur cell Cyclical stability it is poor, the low equal a series of problems of actual specific capacity.
Summary of the invention
In view of this, the diaphragm that the lithium-sulfur cell uses can overcome above-mentioned biography it is necessory to provide a kind of lithium-sulfur cell The shortcomings that system lithium-sulfur cell diaphragm.
A kind of lithium-sulfur cell a comprising cathode, an anode, a lithium-sulfur cell diaphragm and electrolyte, the electrolyte level Between cathode and anode, the lithium-sulfur cell diaphragm setting between a cathode and an anode, is located in electrolyte, wherein described Lithium-sulfur cell diaphragm includes a basic diaphragm and a functional layer, the functional layer include multiple MoP2Nano particle and multiple stones Black alkene piece, the multiple MoP2Nano particle and multiple graphene films are mutually mixed and are uniformly distributed, between multiple graphene film It mutually overlaps or is stacked, the integral graphene layer of shape, the multiple MoP2Nano particle is attached to multiple graphenes The surface of piece, when the lithium-sulfur cell diaphragm is applied to lithium-sulfur cell, the cathode setting of the functional layer face lithium-sulfur cell.
Compared to the prior art, in lithium-sulfur cell provided by the invention, lithium-sulfur cell diaphragm is by MoP2Nano particle and stone The surface of basic diaphragm, MoP are arranged in as functional layer for black alkene material2Nano particle can capture more vulcanizations as catalyst Object, and polysulfide activity of conversion is improved in lithium-sulfur cell charge/discharge process；The graphene film is used as conductive particle, Electronics access abundant is provided for lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the lithium-sulfur cell diaphragm that first embodiment of the invention provides.
Fig. 2 is the lithium-sulfur cell structural schematic diagram using lithium-sulfur cell diaphragm in Fig. 1 that first embodiment of the invention provides
Fig. 3 is MoP of the lithium-sulfur cell that provides of first embodiment of the invention in lithium-sulfur cell diaphragm functional layer2Nanometer The asynchronous charge-discharge performance of grain density.
Fig. 4 is that the constant current charge-discharge of the lithium-sulfur cell in the lithium-sulfur cell and comparative example of first embodiment of the invention recycles survey Test result comparison diagram.
Fig. 5 is charge and discharge electricity of the lithium-sulfur cell in 0.2C in the lithium-sulfur cell and comparative example of first embodiment of the invention Press indicatrix.
Fig. 6 is that the lithium-sulfur cell in the lithium-sulfur cell and comparative example of first embodiment of the invention is put with the current density of 0.2C The corresponding specific capacity in high platform area when electric.
Fig. 7 is that lithium-sulfur cell in comparative example cathode and anode when discharging into 2.08V correspond to the Raman of intermediate product Spectrogram.
Fig. 8 is among lithium-sulfur cell in first embodiment of the invention cathode and anode when discharging into 2.08V are corresponding The Raman spectrum of product.
The structural schematic diagram of lithium-sulfur cell diaphragm in the lithium-sulfur cell that Fig. 9 provides for second embodiment of the invention.
The structural schematic diagram of lithium-sulfur cell diaphragm in the lithium-sulfur cell that Figure 10 provides for third embodiment of the invention.
Main element symbol description
Lithium-sulfur cell 10
Cathode 20
Anode 30
Lithium-sulfur cell diaphragm 100；200；300
Basic diaphragm 102；202；302
Functional layer 104；204；304
Carbon nano tube structure skeleton 106；
MoP2Nano particle 108；208；308
Carbon nanotube 210
Graphene film 312
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
The technical program embodiment is described in further detail below with reference to drawings and the specific embodiments.
Referring to Fig. 1, first embodiment of the invention provides a lithium-sulfur cell 10, which includes a cathode 20, One anode 30, a lithium-sulfur cell diaphragm 100 and electrolyte (not shown).The electrolyte level is between cathode 20 and anode 30. The lithium-sulfur cell diaphragm 100 is arranged between cathode 20 and anode 30, is located in electrolyte.The lithium-sulfur cell diaphragm 100 It is stacked including a basic diaphragm 102 and a functional layer 104.104 face cathode 20 of the functional layer setting, that is, functional layer 104 are located between cathode 20 and basic diaphragm 102.In the present embodiment, the functional layer 104 is by cathode 20 and basic diaphragm 102 Clamped, functional layer 104 is bonded the surface setting of cathode 20.That is, a surface phase mutual connection of the functional layer 104 and cathode 20 Touching.
The cathode 20 is the substance of sulfur-bearing, can be sulphur simple substance or the composite material containing sulphur simple substance.The present embodiment In, cathode 20 is sulphur simple substance, forms a layer structure on the surface of a collector.The anode 30 can be lithium metal, this In embodiment, anode 30 is metal lithium sheet.The electrolyte can be solid-state electrolytic solution, or liquid electrolyte.Electrolysis The material of liquid can choose common electrolyte material in lithium-sulfur cell in the prior art, will not enumerate herein.This implementation In example, it is by double trifluoromethanesulfonimide lithiums (LiTFSI) and lithium nitrate (LiNO that electrolyte, which is by concentration,3) it is dissolved in 1,3- bis- The in the mixed solvent of oxygen pentane (DOL) and glycol dimethyl ether (DME) formed mixed solution, wherein 1,3- dioxolane and The volume ratio of the in the mixed solvent of glycol dimethyl ether, 1,3- dioxolane and glycol dimethyl ether is 1:1；The mixed solution In, the concentration of double trifluoromethanesulfonimide lithiums is 1.0mol/L, and the concentration of lithium nitrate is 0.1mol/L.
Fig. 2 is referred to, the lithium-sulfur cell diaphragm 10 includes a basic diaphragm 102 and a functional layer 104.The basis Diaphragm 102 is a flat surface structure, is to have certain thickness film.It is described basis diaphragm 102 have a first surface and with The second surface that the first surface is oppositely arranged.First surface face cathode 20 is arranged, and second surface face anode 30 is arranged.Institute State the setting of functional layer 104 on the first surface.Functional layer 104 is located between cathode 20 and the first surface of basic diaphragm 102.
The basis diaphragm 102 can be MIcroporous polyolefin film, such as polypropylene (PP) film, polyethylene (PE) film or both Multilayer complex films.The basis diaphragm 102 has multiple micropores.In the present embodiment, the basis diaphragm 102 is porous poly- third Alkene film, with a thickness of 25 microns.
The functional layer 104 includes a carbon nano tube structure skeleton 106 and multiple MoP2Nano particle 108.That is, the function Ergosphere 104 is a CNT/MoP2Layer.The carbon nano tube structure skeleton 106 includes multiple carbon nanotubes, multiple MoP2Nanometer Grain 108 is adsorbed on the surface of multiple carbon nanotube and is supported by the carbon nano tube structure skeleton 106.In some embodiments In, the functional layer 104 only includes carbon nanotube and MoP2Nano particle 108 does not contain other materials.The functional layer 104 Integral thickness be 3~5 microns.
The carbon nano tube structure skeleton 106 is a porous reticular structure, including multiple micropores.The carbon nanotube knot Structure skeleton 106 includes multiple equally distributed carbon nanotubes.The carbon nanotube, which is uniformly distributed, refers to carbon nano tube structure skeleton The quantity of carbon nanotube in 106 in unit area is essentially identical, and carbon nano tube structure skeleton 106 is in the thickness base of every bit This is identical.The carbon nano tube structure skeleton 106 can be the pure nano-carbon tube structure being made of multiple carbon nanotubes.The carbon nanometer Pipe can be one or more of single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube.The carbon nano tube structure It can be combined closely by Van der Waals force between carbon nanotube in skeleton 106.Carbon in the carbon nano tube structure skeleton 106 is received Mitron is unordered or ordered arrangement.Here the orientation of disorderly arranged finger carbon nanotube is irregular, ordered arrangement here Refer to that the orientation of at least most carbon nanotubes has certain rule.Specifically, when carbon nano tube structure skeleton 106 includes unordered When the carbon nanotube of arrangement, carbon nanotube can mutually be wound or isotropism arrangement；When carbon nano tube structure skeleton 106 wraps When including the carbon nanotube of ordered arrangement, carbon nanotube is in one direction or multiple directions are arranged of preferred orient.The carbon nanotube The thickness of structural framework 106 is unlimited, can be 0.5 nanometer~1 centimetre, it is preferable that the thickness of the carbon nano tube structure skeleton 106 It can be 1 micron~10 microns.The carbon nano tube structure skeleton 106 may include at least one layer of carbon nanotube membrane, carbon nanometer Pipe waddingization film or carbon nanotube laminate.
The carbon nanotube membrane includes multiple by Van der Waals force carbon nanotube interconnected.Carbon nanotube membrane can be with For the pure structure being made of carbon nanotube.The multiple carbon nanotube is arranged of preferred orient in the same direction substantially.It is described preferentially Orientation refers to the whole extending direction of most of carbon nanotubes in carbon nanotube membrane substantially in the same direction.Moreover, described The whole extending direction of most of carbon nanotubes is basically parallel to the surface of carbon nanotube membrane.Further, the carbon nanometer Most carbon nanotubes are joined end to end by Van der Waals force in pipe membrane.Specifically, substantially towards same in the carbon nanotube membrane Each carbon nanotube and carbon nanotube adjacent in the direction of extension pass through model moral in most of carbon nanotubes that one direction extends Hua Li joins end to end.Certainly, there is the carbon nanotube of a small number of random alignments in the carbon nanotube membrane, these carbon nanotubes are not The overall orientation of most of carbon nanotubes in carbon nanotube membrane can be arranged to make up and be significantly affected.The carbon nanotube membrane is The film of one self-supporting.The self-supporting is the carrier supported that carbon nanotube membrane does not need large area, as long as and opposite both sides mention Itself membranaceous state vacantly can be kept on the whole for support force, i.e., the carbon nanotube membrane is placed in (or being fixed on) interval When on two supporters of one fixed range setting, the carbon nanotube membrane between two supporters can vacantly be kept certainly The membranaceous state of body.The self-supporting mainly passes through to exist in carbon nanotube membrane to join end to end extension continuously through Van der Waals force The carbon nanotube of arrangement and realize.The thickness of the carbon nanotube membrane can be 0.5 nanometer~100 microns, width and length It is unlimited.When carbon nanotube layer includes multilayer carbon nanotube membrane, carbon nanotube in adjacent two layers carbon nanotube membrane is prolonged It stretches the intersecting angle formed between direction and is more than or equal to 0 degree less than or equal to 90 degree, can be 15 degree, 45 degree, 60 degree or 90 degree etc.. In the present embodiment, the carbon nano tube structure skeleton 106 includes that 20 layers of carbon nanotube membrane are stacked, carbon nano tube structure bone Frame 106 with a thickness of 2 microns.
The carbon nanotube waddingization film includes mutual winding and equally distributed carbon nanotube.Carbon nanotube waddingization film can be with For the pure structure being made of carbon nanotube.It attracted each other, wound by Van der Waals force between the carbon nanotube, formed network-like Structure.The length and width of the carbon nanotube waddingization film is unlimited.Since in carbon nanotube waddingization film, carbon nanotube is mutually twined Around, therefore the carbon nanotube waddingization film has good flexibility, and is a self supporting structure, it can be with bending fold at arbitrary shape Shape is without rupturing.The area and thickness of the carbon nanotube waddingization film are unlimited, with a thickness of 1 micron~1 millimeter.
The carbon nanotube laminate includes equally distributed carbon nanotube, and carbon nanotube is in the same direction or different directions It is arranged of preferred orient.Carbon nanotube laminate can be the pure structure being made of carbon nanotube.Carbon nanotube be also possible to it is each to The same sex.Carbon nanotube in the carbon nanotube laminate mutually partially overlaps, and is attracted each other by Van der Waals force, closely In conjunction with.The surface of the growth substrate of carbon nanotube and formation carbon nano pipe array in the carbon nanotube laminate forms a folder Angle beta, wherein β is greater than 0 degree and is less than or equal to 15 degree.It is different according to the mode rolled, the carbon nanometer in the carbon nanotube laminate Pipe has different spread patterns.When rolling in the same direction, carbon nanotube is arranged of preferred orient along a fixed-direction.It can be with Understand, when rolling along different directions, carbon nanotube can be arranged of preferred orient along multiple directions.The carbon nanotube rolls film thickness It is unlimited, it is preferably 1 micron~1 millimeter.
MoP2108 shape of nano particle is unlimited, having a size of nanoscale.The multiple MoP2Nano particle 108 is attached to carbon and receives On nanotube structures skeleton 106, it is attached to the surface of carbon nanotube and is filled in the micropore of carbon nano tube structure skeleton 106.It is excellent Selection of land, the MoP2Nano particle 108 is uniformly distributed on carbon nano tube structure skeleton 106.The MoP2Nano particle 108 exists The multiple MoP on carbon nano tube structure skeleton2Preferably 10~500 nanometers of the diameter of nano particle 108.In the present embodiment, The MoP2The average diameter of nano particle 108 is 100 nanometers.
In the lithium-sulfur cell diaphragm 100, multiple MoP2Surface density (the lithium-sulfur cell of unit area of nano particle 108 MoP in diaphragm 1002The quality of nano particle 108) it is unlimited, it can adjust according to actual needs.Preferably, the multiple MoP2It receives The surface density of rice grain 108 is 0.1mg/cm2~0.6mg/cm2.In the present embodiment, the multiple MoP2The face of nano particle 108 Density is about 0.3mg/cm2, that is, in the lithium-sulfur cell diaphragm 100, multiple MoP2Nano particle 108 and carbon nano tube structure The mass ratio of skeleton 106 is 7.5:1.
The preparation method of the lithium-sulfur cell diaphragm 100 includes: to provide the basic diaphragm 102；In the basic diaphragm 102 surface is laid with the carbon nano tube structure skeleton 106；By MoP2The suspension of nano particle 108 is dropped evenly to be received in carbon On nanotube structures skeleton 106, after dry, multiple MoP2The carbon that nano particle 108 is attached in carbon nano tube structure skeleton 106 is received The surface of mitron.Multiple MoP2Nano particle 108 is located at the surface of carbon nano tube structure skeleton 106 or is filled in carbon nanotube In the micropore of structural framework 106.
Lithium-sulfur cell 10 provided by the present invention applies a kind of special diaphragm, i.e. lithium-sulfur cell diaphragm 100.The lithium sulphur Battery diaphragm 100 include a basic diaphragm 102 and with a functional layer 104.The functional layer 104 includes carbon nano tube structure bone Frame 106 and multiple MoP2Nano particle 108, and the cathode 20 of lithium-sulfur cell 10 described in 104 face of functional layer is arranged.In lithium sulphur In the charge and discharge process of battery 10, multiple MoP2Nano particle 108 is used as fixative, generates chemistry with the polysulfide of dissolution and makees With to achieve the effect that adsorb polysulfide；Meanwhile and MoP2Nano particle 108 also improves polysulfide as catalyst Redox reaction, be further reduced the content of polysulfide in electrolyte.In addition, 106 conduct of carbon nano tube structure skeleton Support frame is used to support multiple MoP2 nano particles 108, it is ensured that it is uniformly distributed；Carbon nano tube structure skeleton 106 is in physics On also counteract polysulfide migrate.Simultaneously as the good electric conductivity of carbon nanotube, carbon nano tube structure skeleton 106 with One surface of cathode 20 contacts, and it is abundant as providing for cathode 20 that carbon nano tube structure skeleton 106 is also considered as current-collector Electronics access, reduce the internal charge transfer resistance of lithium-sulfur cell.Test result is shown, using the lithium-sulfur cell diaphragm 100 10 cycle performance of lithium-sulfur cell significantly improves, and in 100 circulations, the capacity attenuation that when 0.2C recycles every time is 0.152%；In 500 circulations, the capacity attenuation that when 1C recycles every time is 0.025%.In-situ Raman spectrum also demonstrates lithium The suction-operated to polysulfide of functional layer 104 in sulphur battery diaphragm 100 and MoP2Nanoparticle is in charge and discharge process Catalytic action.
Refer to Fig. 3, it is notable that MoP2The surface density of nano particle 108 is also the electricity for influencing lithium-sulfur cell 10 The important parameter of chemical property.In the identical situation of initial capacitance of cathode 20, after 100 circulations, lithium-sulfur cell diaphragm Middle MoP2(0.1mg/cm when 108 surface density of nano particle is lower2), the capacitance fade of cathode 20 to 783.9mAh/g；Lithium-sulfur cell MoP in diaphragm2(0.6mg/cm when 108 surface density of nano particle is higher2), the capacity of cathode 20 decays to 657.5mAh/g；Lithium sulphur MoP in battery diaphragm2(0.3mg/cm when 108 surface density of nano particle is in median2), the capacity of cathode 20 decays to 905.4mAh/g.This illustrates MoP2Not the higher the better or more lower better for the surface density of nano particle 108.Cause such case The reason of be: when surface density is lower, the absorption of polysulfide may be not exclusively；And when surface density is higher, more sulphur of absorption The amount of compound is likely difficult to desorb, because interaction is strong.MoP provided in the present invention2The surface density of nano particle exists 0.1mg/cm2To 0.6mg/cm2Between be a preferred range.
Hereinafter, the present invention will be with lithium traditional provided in lithium-sulfur cell 10 provided in the present embodiment and comparison lithium Contrast test result illustrates that lithium-sulfur cell diaphragm 100 provided by the present invention proposes lithium-sulfur cell performance between sulphur battery It rises.In Fig. 4~Fig. 8, MoP2Curve corresponding to/CNT middle layer diaphragm represents lithium-sulfur cell 10 provided by the present embodiment, former Curve corresponding to beginning diaphragm represents tradition lithium-sulfur cell provided by comparative example.Wherein, lithium provided by the embodiment of the present invention The diaphragm of sulphur battery 10 uses lithium-sulfur cell diaphragm 100, that is, includes the basic diaphragm 102 and the functional layer 104；Comparative example Provided in traditional lithium-sulfur cell directly adopt diaphragm of the basic diaphragm as battery, do not contain functional layer, other features with The feature of lithium-sulfur cell 10 provided by the embodiment of the present invention is identical.
Fig. 4 is the constant current charge-discharge loop test knot of the lithium-sulfur cell in the lithium-sulfur cell and comparative example of the embodiment of the present invention Fruit comparison diagram.From this figure, it can be seen that lithium-sulfur cell provided by the embodiment of the present invention is shown than lithium sulphur traditional in comparative example The higher circulation conservation rate of battery.Lithium-sulfur cell in the embodiment of the present invention is initially 1223.2mAh/g than discharge capacity, 100 Capacity attenuation is to 905.4mAh/g, capacity retention ratio 74.02% after secondary circulation；And after second of electric discharge, each period Capacity attenuation rate is only 0.152%.And after tradition lithium-sulfur cell provided in comparative example is recycled at 100 times, battery capacity is kept Rate is 33.2% (360mAh/g).It can be seen that lithium-sulfur cell provided by the embodiment of the present invention has better cycle performance, It is enough to illustrate sulphur sulphur battery diaphragm provided by the present invention to the castering action of entire cycle performance of battery.
Fig. 5 is that charging/discharging voltage of the lithium-sulfur cell in 0.2C in the lithium-sulfur cell and comparative example of the embodiment of the present invention is special Levy curve.In the voltage characteristic curve, the multistage reduction of two platform surface sulphur.Platform when platform when charging and electric discharge Between voltage delay Δ E be electrochemical reversibility in battery system important indicator.It can be seen from the figure that institute in comparative example The Δ E value of the lithium-sulfur cell of offer is 0.32V；The Δ E value of lithium-sulfur cell provided by the embodiment of the present invention is 0.25V.Lithium sulphur The Δ E value of battery is lower, illustrates that inside battery polarization situation is weaker, also better for the high rate performance of battery.The present invention is real The reduction for applying the Δ E value of lithium-sulfur cell provided by example is primarily due in lithium-sulfur cell diaphragm, MoP2The presence of nano particle Improve the activity of conversion of polysulfide.
Fig. 6 is the lithium-sulfur cell in the lithium-sulfur cell and comparative example of the embodiment of the present invention with 0.2C's (1C=1600mA/g) The corresponding specific capacity in high platform area when current density is discharged.In lithium-sulfur cell, corresponding high platform area capacity is that elemental sulfur S turns Turn to Li2S4Process, this part specific capacity is higher, illustrates that lithium-sulfur cell diaphragm imitates the inhibition of the shuttle effect of polysulfide Fruit is better.As seen from Figure 6, in lithium-sulfur cell provided by the embodiment of the present invention, lithium-sulfur cell diaphragm is to polysulfide Shuttle effect has better inhibitory effect.
Fig. 7 is that lithium-sulfur cell in comparative example cathode and anode when discharging into 2.08V correspond to the Raman of intermediate product Spectrogram.For the lithium-sulfur cell in the embodiment of the present invention, cathode and anode when discharging into 2.08V correspond to intermediate product to Fig. 8 Raman spectrogram.For the lithium-sulfur cell in comparative example, it can be seen from figure 7 that can be observed in cathode and anode two sides To Li2S6And Li2S2Peak, illustrate the Li that the cathode of battery and anode two sides have2S6And Li2S2Substance, lithium-sulfur cell diaphragm do not have Play the role of playing the shuttle effect for inhibiting polysulfide.For lithium-sulfur cell provided by the embodiment of the present invention, Li2S6With Li2S2Peak only arrived in the unilateral observation of cathode, there is not the peak of polysulfide in anode, this illustrates in the embodiment of the present invention Lithium-sulfur cell diaphragm there is good inhibiting effect to the shuttle effect of polysulfide.
Second embodiment of the invention provides a lithium-sulfur cell, which includes a cathode, an anode, a lithium-sulfur cell Diaphragm and electrolyte.The electrolyte level is between cathode and anode.Lithium-sulfur cell diaphragm setting cathode and anode it Between, it is located in electrolyte.The lithium-sulfur cell diaphragm includes that a basic diaphragm and a functional layer are stacked.The functional layer is just Cathode is arranged, that is, functional layer is located between cathode and basic diaphragm.Lithium-sulfur cell provided by the present embodiment and first is implemented 10 structure of lithium-sulfur cell in example is essentially identical, the difference is that the part-structure of lithium-sulfur cell diaphragm.
Fig. 9 is referred to, lithium-sulfur cell diaphragm 200 provided in second embodiment includes a basic diaphragm 202 and one Functional layer 204.The basis diaphragm 202 is a flat surface structure, is to have certain thickness film.The basis diaphragm 202 has The second surface for having a first surface and being oppositely arranged with the first surface.First surface face cathode 20 is arranged, the second table Face face anode 30 is arranged.The functional layer 204 is arranged in first surface, positioned at the first table of cathode 20 and basic diaphragm 202 Between face.
The functional layer 204 includes multiple MoP2Nano particle 208 and multiple carbon nanotubes 210.The multiple MoP2Nanometer Particle 208 and multiple carbon nanotubes 210 are mutually mixed and are uniformly distributed.It can mutually be wound between multiple carbon nanotubes 210.It is described MoP2Nano particle 208 can also be wound by carbon nanotube 210.The multiple MoP2Nano particle 208 and multiple carbon nanotubes 210 can be interconnected to form an overall structure by Van der Waals force.In the lithium-sulfur cell diaphragm 200, multiple MoP2Nanometer Surface density (the MoP in the lithium-sulfur cell diaphragm 200 of unit area of particle 1082The quality of nano particle 208) unlimited, Ke Yigen It is adjusted according to actual needs.Preferably, the multiple MoP2The surface density of nano particle 208 is 0.1mg/cm2~0.6mg/cm2。
In some embodiments, the functional layer 204 only includes multiple MoP2Nano particle 208 and multiple carbon nanotubes 210, do not contain other materials.In further embodiments, the functional layer 204 can further include carbon black and graphene Equal conductive particles.Selectively, functional layer 204 can further include binder, for fixing multiple MoP2Nano particle 208 and multiple carbon nanotubes 210.
The preparation method of the lithium-sulfur cell diaphragm 100 includes: to prepare MoP2Nano particle 208 and carbon nanotube 210 Mixed liquor stirs evenly；One basic diaphragm 102, MoP is provided2Nano particle 208 and the mixed liquor of carbon nanotube 210 are coated in The surface of basic diaphragm 102 forms functional layer after dry.
In addition to features described above, lithium-sulfur cell 10 provided by lithium-sulfur cell provided by second embodiment and first embodiment Other structures it is identical with performance, no longer repeat one by one again.
Third embodiment of the invention provides a lithium-sulfur cell, which includes a cathode, an anode, a lithium-sulfur cell Diaphragm and electrolyte.The electrolyte level is between cathode and anode.Lithium-sulfur cell diaphragm setting cathode and anode it Between, it is located in electrolyte.The lithium-sulfur cell diaphragm includes that a basic diaphragm and a functional layer are stacked.The functional layer is just Cathode is arranged, that is, functional layer is located between cathode and basic diaphragm.Lithium-sulfur cell provided by the present embodiment and first is implemented 10 structure of lithium-sulfur cell in example is essentially identical, the difference is that the part-structure of lithium-sulfur cell diaphragm.
Referring to Figure 10, the lithium-sulfur cell diaphragm 300 in 3rd embodiment includes a basic diaphragm 302 and a functional layer 304.The basis diaphragm 302 is a flat surface structure, is to have certain thickness film.The basis diaphragm 302 has one the One surface and the second surface being oppositely arranged with the first surface.First surface face cathode 20 is arranged, second surface face Anode 30 is arranged.The functional layer 304 is arranged in first surface.The functional layer 304 is located at cathode 20 and basic diaphragm 302 Between first surface.
The functional layer 304 includes multiple MoP2Nano particle 308 and multiple graphene films 312.The multiple MoP2Nanometer Particle 308 and multiple graphene films 312 are mutually mixed and are uniformly distributed.It can mutually be overlapped between multiple graphene films 312 or layer Folded setting, the integral graphene layer of shape.The multiple MoP2Nano particle 308 is attached to the table of multiple graphene films 312 Face.In some embodiments, the functional layer 304 only includes MoP2Nano particle 308 and graphene film 312 do not contain other Material.
Graphene film 312 in the graphene layer is connected with each other by Van der Waals force.Graphene in the graphene layer The arrangement mode of piece 312 can for mutually overlapping setting, be set side by side or the setting that overlaps.Graphene film has good Electric conductivity.The thickness of the graphene film 312 is less than or equal to 100 nanometers.In the present embodiment, graphene film 312 with a thickness of 0.5 nanometer to 100 nanometers.The thickness with a thickness of single-layer graphene film 312 of the graphene layer is to 1 millimeter.
In the lithium-sulfur cell diaphragm 300, multiple MoP2Surface density (the lithium-sulfur cell of unit area of nano particle 108 MoP in diaphragm 2002The quality of nano particle 208) it is unlimited, it can adjust according to actual needs.Preferably, the multiple MoP2It receives The surface density of rice grain 208 is 0.1mg/cm2~0.6mg/cm2。
The preparation method of the lithium-sulfur cell diaphragm 300 is the following steps are included: firstly, provide a certain amount of graphene oxide The graphene oxide sheet is placed in a solvent and forms a mixture by piece；The sonic oscillation mixture, keeps graphene oxide sheet equal Even dispersion simultaneously is suspended in the solvent to obtain a graphene oxide sheet dispersion liquid；The graphene film dispersion liquid is passed through into pumping The mode of filter forms graphene layer；Graphene layer is transferred to the surface of basic diaphragm 302；By MoP2Nano particle 308 hangs Turbid drops evenly on graphene layer, after dry, multiple MoP2Nano particle 108 is attached to the graphene film in graphene layer 312 surface or between graphene film 312.
In the lithium-sulfur cell diaphragm 300, multiple MoP2Nano particle 308 and multiple graphene films 312 are uniformly distributed；Institute Multiple graphene films 312 are stated mutually to overlap or be stacked the graphene layer to be formed that electrolyte can be made to pass through is same When, physically also counteract that polysulfide migrates.
In addition to features described above, lithium-sulfur cell 10 provided by lithium-sulfur cell provided by 3rd embodiment and first embodiment Other structures it is identical with performance, no longer repeated one by one secondary.
In addition, those skilled in the art can also do other variations in spirit of that invention, these are spiritual according to the present invention The variation done should be all included in scope of the present invention.

Claims (10)

1. a kind of lithium-sulfur cell, including a cathode, an anode, a lithium-sulfur cell diaphragm and electrolyte, the electrolyte level is in yin Between pole and anode, the lithium-sulfur cell diaphragm setting between a cathode and an anode, is located in electrolyte, which is characterized in that institute It includes multiple MoP that lithium-sulfur cell diaphragm, which is stated, including a basic diaphragm and a functional layer, the functional layer2Nano particle and multiple Graphene film, the multiple MoP2Nano particle and multiple graphene films are mutually mixed and are uniformly distributed, multiple graphene film it Between mutually overlap or be stacked, the integral graphene layer of shape, the multiple MoP2Nano particle is attached to multiple graphite The surface of alkene piece, when the lithium-sulfur cell diaphragm is applied to lithium-sulfur cell, the cathode setting of the functional layer face lithium-sulfur cell.
2. lithium-sulfur cell as described in claim 1, which is characterized in that it is described basis diaphragm include a first surface and with this The second surface that first surface is oppositely arranged, the setting of cathode described in the first surface face, lithium sulphur described in second surface face The anode of battery is arranged, and the functional layer is arranged on the first surface, between cathode and the first surface of basic diaphragm.
3. lithium-sulfur cell as claimed in claim 2, which is characterized in that the functional layer and a surface of the cathode are mutual Contact.
4. lithium-sulfur cell as described in claim 1, which is characterized in that the graphene film in the graphene layer passes through Van der Waals Power is connected with each other.
5. lithium-sulfur cell as described in claim 1, which is characterized in that the arrangement mode of the graphene film in the graphene layer For mutually overlapping setting, it is set side by side or the setting that overlaps.
6. lithium-sulfur cell as described in claim 1, which is characterized in that the graphene film is received with a thickness of 0.5 nanometer to 100 Rice.
7. lithium-sulfur cell as described in claim 1, which is characterized in that the multiple MoP2The diameter of nano particle is 10~500 Nanometer.
8. lithium-sulfur cell as described in claim 1, which is characterized in that the multiple MoP2The surface density of nano particle is 0.1mg/cm2~0.6mg/cm2。
9. lithium-sulfur cell as described in claim 1, which is characterized in that the functional layer with a thickness of 2~5 microns.
10. lithium-sulfur cell as described in claim 1, which is characterized in that the functional layer is by graphene film and MoP2Nano particle Composition.
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